Polyphosphites and process of making same



United States Patent ()fifice 3,341,629 Patented Sept. 12, 1967 New Jersey No Drawing. Filed Jan. 24, 1966, Ser. No. 522,395 18 Claims. (ill. 269-923) ABSTRACT OF THE DISCLQSURE Polymeric phosphites are prepared by reacting a hydrogenated dihydric phenol or an aromatic dihydric alcohol with a tertiary alkyl aryl or halo aryl phosphite and stopping the condensation when 50 to 90%, most preferably 65 to 75%, of the theoretical amount of monohydric alcohol or phenol is formed. The most preferred material is that made from hydrogenated bis phenol-A and triphenyl phosphite in which the product obtained has 6.3 to 6.8% phosphorus. The phosphites are useful in stabilizing halogen containing polymers (particularly vinyl chloride resins) and hydrocarbon polymers and also are useful as flameproofing agents for hydrocarbon polymers, cellulose and cellulose esters.

This application is a continuation-in-part of application Ser. No. 376,202, filed June 18, 1964, and is a continuation-in-part of application Ser. No. 366,891, filed May 12, 1964.

This invention relates to novel phosphite polymers.

In the thermoplastics industry, stabilization of the thermoplastic resins, e.g. polyvinyl chloride and polypropylene, by the use of barium, cadmium, zinc, tin, lead and phosphite systems to prevent degradation from heat, light and weathering has contributed to the rapid growth into markets which were earlier closed to many plastics and has also greatly accelerated the rate of growth in many established areas.

The incorporation of liquid organic phosphites, e.g. see Leistner Patent No. 2,564,646, in stabilizing vinyl chloimprovements. However, in many cases the liquids are dimcult or impossible to use and as a result many attempts have been made to prepare the organic phosphite in solid form,

present invention to make novel examples, while indicatin preferred embodiments of the invention, are given by Way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that the objects can be attained 'by reacting a trihydrocarbyl phosphite or trihaloaryl phosphite with an aromatic dihydric alcohol or more preferably with a hydrogenated dihydric phenol, i.e. a dihydric alcohol resulting from the hydrogenation of a dihydric phenol (also called a hydrogenated bisphenol).

phenyl phosphite, didecyl phosphite,

(Z-methylphenyl) phosphite, di (4-dodecylphenyl) phosphite, di-(Z-chlorophenyl) phosphite, di (2, 4-dimethylphenyl) phosphite, di (4-bromophenyl) phosphite, diethyl phosphite, dicyclohexyl phosphite, diocta- As the trihydrocarbyl or trihaloaryl phosphite reactant there can be used triphenyl phosphite, tris (Z-rnethylphenyl) phosphite; tris (3-methylphenyl) phosphite, tris (4-methylphenyl) phosphite, tris (Z-ethylphenyl) phosphite, isopropylphenyl) phosphite, tris (4-dodecylphenyl) phosphite, tris (2,4-dimethylphenyl) phosphite, tris (Z-chlorophenyl) phosphite, tris (Z-bromophenyl) phosphite, tris (2-fluorophenyl) phosphite, tris (4-t-butylphenyl) phosphite, tris decyl phosphite, tris octyl phosphite, tris (alpha naphthyl) phosphite, diphenyl 4-methylphenyl phosphite. The. preferred phosphite reactants are triaryl phosphites, most preferably triphenyl phosphite.

As aromatic dihydric alcohols there can be used p- Xylylene glycol, m-Xylylene glycol, o-xylylene glycol and 1,4-cyclohexanedimethanol.

As the hydrogenated dihydric phenol there can be used 4,4'-isopropylidene dicyclohexanol (also called of diol, e.g. hydrogenated bisphenol A.

The reaction can be continued until a cross linked or highly branched polymer is formed. Preferably, however, the reaction is A and triphenyl phosphite, the reaction is stopped while the product has 63-68% phosphorus by weight. Thus, under the preferred conditions, the reaction is stopped when 65-75% of the theoretical amount of phenol derived from the triphenyl phosphite or the like is removed by distillation.

The reaction can be continued until of the theoretical amount phite) as been recovered but this is not preferred since continued muchbeyond they point of 6.8% phosphorus content in the polymer, gel-like, i.e. cross linked materials, are formed rather than the preferred thermoplastic materials. The reaction is normally carried out with the aid of heat. The reaction can be continued as long as the phenol by-product is removed. Conveniently the phenol formed is removed by vacuum equivalent to 15 mm. absolute pressure or less.

Linear materials can be formed having the formula where R is the divalent residue or (a) bis (hydroxyalkyl) benzenes, or (b) the hydrogenateddihydric phenol, and R is aryl, haloaryl or alkyl and n is an integer of 1 or more, e.g., 10, 50 or 200.

Nelson Patent No. 2,612,488 shows making phosphite polymers from dihydric phenols. The procedure of Nelson involving the use of phosphorus trichloride or the like creates problems in obtaining a pure halogen free product, particularly if the reaction is stopped prior to completion. The Nelson procedure also cannot be employed with the cycloaliphatic dihydric alcohols employed in the present invention because the alcohols react with phosphorus trichloride or the like to form organic halides. These in turn can react further to form phosphonates rather than the desired thermoplastic polymeric phosphites.

The products obtained according to the invention are brittle solid resins at room temperature. They can be readily ground forincorporation in an amount of 0.01 to 20% into halogen containing resins, e.g. vinyl chloride resins, as stabilizers against heat and light. They can .also be incorporated in an amount of 0.01 to 20% as stabilizers for hydrocarbon polymers such as polyethylene, polypropylene, ethylene-propylene copolymers (e.g. a 50:50 copolymer), polystyrene, acrylonitrile-butadiene-styrene terpolymer, natural rubber, rubbery butadiene-styrene copolymer, polybutadiene, polyisobutylene, isobutylene-butadiene copolymer (butyl rubber) and the like. In some instances, it is desirable to also incorporate a phenolic antioxidant such as 2,2-methylene bis (4-methyl-6-t-butyl phenol) or 2,4,6-tri-t-butyl phenol.

The products can also be used as antioxidants with barium, cadmium and zinc salts and synergistic activity has been noted in this connection. Thus there can be included 1-10% of salts such as barium-cadmium laurate, zinc stearate, cadmium Z-ethylhexoate, barium nonylphenolate barium octylphenolate, barium stearate, zinc octoate in the antioxidant formulations.

Theresins of the present invention can also be incorporated in an amount of 1 to 50% terials to give improved flame and/or fire resistance. Thus they can be used to improve the fire resistance of cellulose, cellulose acetate, cellulose nitrate, cellulose acetate-butyrate, polystyrene, polyethylene, polypropylene and other polymeric monoolefins.

The resins of the present invention are also suitable to form cast or molded articles, e.g. disposable cups.

The initial heating for the reaction is preferably done slowly to avoid an explosion. After initial reaction at about 100 to 110 C., the reaction mass is heated above 150 C., e.g. to 180 C., and then vacuum distilled to remove the by-product phenol.

Unless otherwise indicated, are by weight.

all parts and percentages EXAMPLE 1 240 parts of hydrogenated bisphenol A, 341 parts of triphenyl phosphite, 84 parts of t-octylphenol and 6 parts of diphenyl phosphite were mixed and subjected to vacuum distillation until the temperature reached 214 C. with a vacuum of 29.5 inches. 222 parts of distillate were removed. The residue was a solid polymer with a phosin other plastic ma-.

phorus content of 7.6%. It was compatible in resins,

e.g. polyvinyl chloride, and polypropylene and natural and synthetic rubbers and exerted a stabilizing effect. It was particularly eifective in combination with conventional stabilizing systemssuch as phenols and barium and cadmium soaps.

EXAMPLE 2 775 parts of triphenyl phosphite, 480 parts of hydrogenatedbisphenol A and 10 parts of diphenyl phosphite were mixed and subjected to vacuum distillation. Terminal conditions were 208 C. and 29.5 inches of vacuum. 363 parts of phenol were removed from the system. The residue was, a resinous polymer with a phosphorus content of 8.7%

EXAMPLE 3 341 parts of triphenyl phosphite, 240 parts of hydrogenated bisphenol A, and 6 parts of diphenyl phosphite were mixed and subjected to vacuum distillation. Terminal conditions were 216 C. and 29.5 inches of vacuum. The residue was a resinous polymer with a phosphorus content of 8.4%.

EXAMPLE 4 1860 parts of triphenyl phosphite, 2160 parts of hydrogenated bisphenol A and24 parts of diphenyl phosphite were mixed and subjected to vacuum distillation as in Example 3. 1112 parts of phenol distillate were removed. The residue was a hard amber-colored resin with a phosphorus content of 6.3%. ferred ones according to the invention and was compatible with and displayed antioxidant activity in stabilizing plastics, e.g. polyvinyl chloride, polyethylene, polypropylene, natural rubber and synthetic rubber. It was particularly effective in plastics when used in combination with conventional barium, zinc and cadmium stabilizers.

EXAMPLE 5 62 parts of triphenyl phosphite were mixed with 41 parts of p-xylylene glycol. The temperature was maintained in the temperature range, to C. for 20 minutes. The glycol dissolved slowly to give a clear viscous liquid. The temperature was then slowly raised to C. and finally to 220 C. The product was finally distilled under 5 mm. Hg pressure at 200 C. The final product was a light colored, brittle solid, at room temperature and has a phosphorus content of 11%.

EXAMPLE 6 240 parts of hydrogenated bisphenol A, 326 parts of triphenyl phosphite and 4 parts of diphenyl phosphite were mixed and subjected to vacuum distillation. Terminal conditions were 210 C. and 29.5 inches of vacuum. A total of 170 parts of phenol were removed by the distillation. The. product was a hard polymer with a phosphorus content of 8.1%.

EXAMPLE 7 341 parts of triphenyl phosphite, parts of 1,4-cyclohexanedimethanol and 6 parts of diphenyl. phosphite were mixed and subjectedto vacuum distillation. Terminal conditions were 158 C. and 5 mm. Hg absolute pressure. 210 parts of distillate were removed. vThe prod uct was a clear white solid resinous ploymer with a phosphorus content of 12%.

EXAMPLE 8 2160 parts of hydrogenated bisphenol A, 1860 parts of triphenyl phosphite and 24 parts of diphenyl phosphite were mixed and subjected to vacuum distillation. Terminal conditions were 205 C. and 29.5 inches of vacuum. 1140 parts of distillate were removed. The still residue was a clear solid resin with a phosphorus content of 6.4%. This product is one of the preferred ones according to the invention.

The product is one of the preafter as a Triad and mate the number of such 5 As indicated a preferred series 0 or polymers is prepared from tri to herein Triad Thus when n is one as in the indicated formula the le p osphorus content is 6.4%

her is 116. In the event that 4.5 mols mols from 2 Triads) the for f solid phosphite resins This unit will be referred phenyl phosphite and hythe letter n used to desig drogenated bisphenol A in which the reactants are used units in the polymer molecule. in the molecular proportions to provide equal mols of replaceable phenol and hydroxyl groups, i.e. 2 mols of 5 mo cular weight is 964, the h TPP) and 3 mols of hydrogenated triphenyl phosphite and the hydroxyl num bisphenol A (HBPA). of phenol are stripped out (9 Varying amounts of phenol are removed from this sysmula of the product is i-ght of 1834, phosphorus content ydroxyl number of t 1 CH phosphorus content, increased having a molecular we ights and decreased amounts of free hyof 6.7% and a h 91. droxyl groups. Thus P with If 4.67 mols of phenol are stripped out (14 mols from stripping out 4 mols of phenol there 25 3 Triads) the formula of the product is tern to provide increased molecular we by reacting the 2 mols of TP 3 mols of HBPA and 612 2L0 OWOWIO nouoomn777 666 ight of 2704, phosphorus content r 1 CH3 products obtained The following table summarizes the g TPP with HBPA in the ratio of 2 mols to 3 TABLE 1 having a molecular we of 6.8% and hydroXyl number of 82.

r by reactin mols:

Phenol Out (Mols) Total Per "11 Triads, n

is formed a first polymer unit which has the followinformula HO OPO EXAMPLE 10' The procedure of Example 4 was repeated using 2112 of tris (4-methylphenyl) phosphite in place of the triphenyl phosphite. There wereremoved, 1280 parts of distillate to give a solid resin.

EXAMPLE 11 1 part of the resin prepared in Example 4 was mixed with 100 parts of vinyl chloride resin (Geon 103 Ep) to give a stabilized composition.

EXAMPLE 12 2 parts of the resin of Example 4 were mixed with parts of solid polypropylene (melt index 0.8).

EXAMPLE 13 1 part of the resin prepared in Example 8 and 2 parts of barium-cadmium laurate were mixed with 100 parts of polyvinyl chloride and 50 parts of dioctyl phthalate to give a stabilized product.

EXAMPLE 14 1 part of the product of Example 9 was mixed with 100 parts of polypropylene (melt index 0.4)

EXAMPLE 1 1 part of the resin prepared in Example 8 and 2 parts of barium-cadmium laurate were mixed with 100 parts of a vinyl chloride-acrylonitrile copolymer (60:40, Dynel).

In place of the vinyl chloride resins mentioned above there can be stabilized other halogen containing polymers such as chlorinated polyethylene having 14 to 75%, e.g. 27% chlorine by weight, polyvinyl chloride, polyvinylidene chloride,polyvinyl bromide, polyvinyl fluoride, copolymers of vinyl chloride with 1 to 90%, preferably 1 to 40%, of a copolymerizable ethylenically unsaturated material such as vinyl acetate, vinyl butyrate, vinyl benzoate, allyl acetate, vinyl stearate, vinylidene fluoride, diethyl fumarate, diethyl maleate and other alkyl fumarates and maleates, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate and other alkyl methacrylates, methyl alpha chloroacrylate, styrene, alpha methyl styrene, trichloroethylene, vinyl etherssuch as vinyl ethyl ether, vinyl chloroethyl ether, vinyl phenyl ether, vinyl ketones such as vinyl methyl ketone and vinyl phenyl ketone, l-fluoro-l-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate, and chloroallylidene diacetate. Typical copolymers include vinylv chloride-vinyl acetate (96:4 sold commercially as VYNW), vinyl chloride-vinyl acetate (87:13), vinyl chloride-vinyl acetatemaleic anhydride (86: 13 :1), vinyl chloride-diethyl fumarate (95:5), vinyl chloride-trichloroethylene (95 :5 vinyl chloride-2-etbylhexyl acrylate (80:20) and vinyl chlorideacrylonitrile (60:40).

where R is the divalent residue of where R is the divalent residue of I claim: 1. A thermoplastic material having the basicstructure a member of the group consisting of (a) his (hydroxy alkyl) benzenes and (b) hydrogenated dihydric phenols, R is selected from the group consisting of aryl, alkyl and haloaryl and n is an integer.

2. A compound according to claim 1 where n is 2.

3. A compound according to claim 2 having the formula 4. A polymer according to claim 1 wherein R is aryl.

5. A branched polymer having the formula HOROPOROlTOROH o o ROPOROPOROH LRlm ROIIOI'KOPOROH a member of the group consisting of (a) bis (hydroxy alkyl) benzenes and (b) hydrogenated dihydric phenols, R is selected from the group consisting of aryl, alkyl and haloaryl, and m is,

' zero or an integer.

6. A polymer according to claim 5 wherein R is'aryl.

7. A polymer according to claim 5 where m is zero.

8. A polymer according to claim 7 wherein R is the residue of 4,4-isopropylidene dicyclohexanol 9. A polymer according to claim 8 wherein R is aryl of the phenyl series.

10. A polymer according to claim 5 where m is 1.

11. A polymer according to claim 10 where R is the residue of 4,4-isopropylidene dicyclohexanol.

12. A polymer according to claim 11 wherein R is aryl of the phenyl series having up to one alkyl group attached to the phenyl nucleus.

13. A polymer according to claim phenyl.

14. A process of preparing an organic condensation product comprising heating 1 mol ofa dihydric compound of the group consisting of (a) bis (hydroxyalkyl) benzenes and (b) hydrogenated dihydric phenols and /3 mol of a phosphite having the formula 12 v wherein R is ing of aryland haloaryl and stopping the reaction when 50 to. of the theoretical amount of the monohydric compounds having the formulae R OH, R OH and R OH have been formed.

15. A process according to claim 14 wherein the reaction -is stopped when 65 to 75% of the theoretical amount of the monohydric compounds have been formed.

16. A process according to claim 14 wherein R is aryl.

References Cited UNITED STATES PATENTS 3,047,608 7/1962 Friedman et a1 260-461 10 FOREIGN PATENTS 1,332,901 7/1963 France.

978,285 12/1964 Great Britain.

OTHER REFERENCES Petrov et a1.: Polymer Science, U.S.S.R. 5, 925932 (1963).

Petrov et 211.: Chem Ab. 61, 5782e (1964).

10 WILLIAM H. SHORT, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,341,629 September 12, 1967 Millard S. Larrison It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 8, lines 29 to 38, the formula should appear as shown below instead of as in the patent:

HOROPOROPOROH Oll OROflOROl-l 0 0 L ROPOROPOROH Signed and sealed this 15th day of October 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A THERMOPLASTIC MATERIAL HAVING THE BASIC STRUCTURE 